Materials and Design 32 (2011) 1717–1732

Contents lists available at ScienceDirect

Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Review

Glasses as engineering materials: A review

Eugen Axinte ⇑
Gh. Asachi Technical University of Iasi, Faculty of Machine Manufacturing & Industrial Management, 59A, Prof. Dimitrie Mangeron Blvd., Romania

a r t i c l e i n f o a b s t r a c t

Article history: Glass products have applications in design engineering, and they can solve many special problems. These
Received 15 September 2010 materials can work in situations in which plastics and metals would fail and need to be part of designer’s
Accepted 24 November 2010 repertoire. In some situations, by using these materials, some difficult problems would be solved. This
Available online 28 November 2010
paper contains a number of chapters as follows: a brief about ceramics family, a short history of glass,
a brief about physics and the technology of glass fabrication, recently developed glasses with special des-
Keywords: tinations, testing methods and news about glass parts processing (grinding, waterjet processing, laser
Glasses
cutting, nanoimprint lithography, etc.). The last chapter of this review paper contain some strategic lines
Constitution
Environmental performance
of glass usage in industry and estimations about the future of glass development.
Ó 2010 Elsevier Ltd. All rights reserved.

1. The ceramics family Glasses are not ceramics (by previous definition of ceramics),
but they are used for similar type of things as ceramics and have
Cermets and ceramics are becoming the tool materials for the some properties that are typical for ceramics. The most common
present and future. By using the cemented carbides at wood work- property of ceramics, glasses, and cements is brittleness.
ing tools (as saw blades, cutting wheels), the wear was reduced sig- The measure of crack propagation tendency, fracture toughness,
nificant. Coated cemented carbides displaced the high-speed steel is lower at ceramics family than at metals, as is shown in Fig. 2.
for cutting tools and also high production press dies use the ce-
mented carbide tooling. Ceramics are taking a lot of high-temper-
ature machine tasks, are substrates for computer chips, and are 2. Brief history of glass: past and present of glass
used for prosthetic devices. Glasses and carbon products have
applications in design engineering and they can solve many special It is not exactly known when, where, or how humans first
problems. learned to make glass. The legends tells us that a Phoenician sailor
These materials can work in situations in which plastics and (by other historians, a Roman sailor), cooking the evening meal on
metals would fail and need to be part of designer’s repertoire; a beach, sets the pots on top of stones of natron (a natural mixture
sometimes, using these materials, some difficult problems would of sodium carbonate decahydrate, sodium bicarbonate along with
be solved. Ceramics are defined as solids composed of compounds small quantities of household salt). As the cooking fire heated both
that contain metallic and/or non-metallic elements, and the atoms these stones and the sand below, an unknown liquid began to flow
of compounds are held together with strong atomic forces (ionic or and that was the origin of man-made glass.
covalent bonds). The spectrum of ceramic uses is presented in In [2] is demonstrated and argued that in ancient times, soda
Fig. 1. glasses with high alumina concentrations are quite rare around
The ceramics with high strength and the best toughness (as alu- the Mediterranean area or in the Middle East. The few available
minum, zirconias, oxides, silicon carbides) were named in 1980 as examples include European Iron-Age dark blue glass colored with
‘‘structural ceramics’’. In Japan, these ceramics were called ‘‘fine cobalt-rich alum that contains up to 8% of alumina. Mineral
ceramics’’. In 1990, the (ASTM) Committee for ceramics (C28) soda–alumina (m-Na–Al) glass has been found across a vast area
named this ceramics ‘‘advanced ceramics’’. The definition given stretching from Africa to East Asia. m-Na–Al glass appears around
by C28 for this class of materials is highly engineered, high-perfor- the 5th c. B.C. and is relatively common for periods as late as the
mance, predominantly non-metallic, inorganic, ceramic material 19th c. A.D. It is particularly abundant in South Asia, where raw
having specific functional attributes (by standard ASTM C1145) [1]. materials to produce m-Na–Al glass are readily available and was
likely manufactured there; however, the number and the impor-
tance of the manufacturing centers are unknown as archaeological
⇑ Tel./fax: +40 232217290 (office), mobile: +40 722892926. information is extremely scarce. The interpretation of data ob-
E-mail address: [email protected] tained using compositional analysis on a large corpus of artifacts
URL: http://www.cm.tuiasi.ro/html/ro/tcm.htm (486) shows that at least five subgroups of m-Na–Al glass can be

0261-3069/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2010.11.057
1718 E. Axinte / Materials and Design 32 (2011) 1717–1732

Fig. 1. The spectrum of ceramics uses.

developed (this period is known as the Second Golden Age of Glass).

In North America (United States), the first factory known was a
glass plant built at Jamestown, Virginia, in 1608, but failed within
a year. The Jamestown colonists tried glassmaking again in 1621,
but an Indian attack in 1622 and the scarcity of workers ended this
attempt in 1624. The glass industry was reestablished in America
in 1739, when Caspar Wistar built a glassmaking plant in Salem
County, New Jersey. This plant operated until 1780.
In 1820, Bakewell, Page, & Bakewell Co. from Pittsburgh, Penn-
sylvania, introduced the first real development in production glass-
blowing since the blowpipe, a development that would change
how glass was used forever. They patented a process of mechani-
cally pressing hot glass. After 1890, glass uses and manufacturing
developments increased so rapidly as to be almost revolutionary.
The late 1900s brought new important specialty glasses. Among
Fig. 2. The fracture toughness of different materials. the new specialty glasses were transparent glass–ceramics, which
are used to make cookware, and chalcogenide glass, an infrared-
identified using the concentrations of calcium, magnesium, transmitting glass that can be used to make lenses for night-vision
uranium, barium, strontium, zirconium, and cesium measured goggles. The science and engineering of glass as a material was
with laser ablation-inductively coupled plasma-mass spectrometry much better understood, and in the late 1950s, Sir Alastair Pilking-
(LA-ICP-MS). From this data, it is possible to infer the existence of ton introduced a new revolutionary production method (float glass
several m-Na–Al glass-making centers, not all of them located in production), by which 90% of flat glass is still manufactured today.
South Asia as previously assumed. They were operating over differ- In the 1970s, optical fibers were developed for use as ‘‘light pipes’’
ent time periods and were connected to different exchange in laser communication systems. These pipes maintain the bright-
networks. ness and intensity of light being transmitted over long distances.
It is historically accepted that the first manufactured glass was Types of glass that can store radioactive wastes safely for thou-
in the form of a glaze on ceramic vessels, about 3000 B.C. The first sands of years were also developed during the 1970s.
glass vessels were produced about 1500 B.C. in Egypt and Mesopo-
tamia. The glass industry was extremely successful for the next 3. Brief about physics of glass: how it is made
300 years and then declined. It was revived in Mesopotamia in
the 700 B.C. and in Egypt in the 500 B.C. For the next 500 years, Generally, solids (metals) have a three-dimensional periodic
Egypt, Syria, and the other countries along the eastern shore of structure (crystalline structure). But also exists solids with a ran-
the Mediterranean Sea were glassmaking centers. Glass manufac- domized three-dimensional structure – these solids are called
turing developed in the Roman Empire and spread from Italy to amorphous or glassy (Fig. 3).
all Roman provinces. The first four centuries of Christian Era is A lot of materials such as organic polymers and metal alloys are
called the First Golden Age of Glass. In the middle ages, by the time able to form under special conditions amorphous structures. An
of the Crusades, glass manufacture had been revived in Murano is- inorganic amorphous or glassy solid is a high-speed cooled liquid
land, near Venice, where soda lime glass, known as crystal, was (cooled fast enough to prevent crystallization).
 E. Axinte / Materials and Design 32 (2011) 1717–1732 1719

Fig. 3. Crystalline structures (a) amorphous randomized structures (b) and the molecular structure of silica-based glass (c).

The relationship between the oxygen and the cation of the oxide
compound essentially influences the glass-forming ability of an
oxide. There are four types of oxides used in glass fabrication
(see Table 1).
At room temperature, glasses are very viscous structures
(1018 Pa  s – glass viscosity vs 1 Pa  s – water viscosity). Viscous
flow of glass at room temperature occurs in a geological timescale.
With increasing temperature, the glass viscosity decreases as is
shown in Fig. 4.
There are five very important temperatures, called ‘‘standard
points’’, associated with the viscous flow (melting) of glass. The
strain point is the maximum temperature supported by glass for
structural applications. A review and the description of standard
points is given by Table 2.
After the glass was formed, it is cooled to a temperature nearly
above the strain point, where it will retain its shape and resist flow.
At this point, the glass parts are annealed to relieve the internal
stresses. A glass part that is incorrectly annealed will fracture or
crack at ambient temperature.
The behavior of specific density of glass as a function of the
temperature is illustrated by graph from Fig. 5.
It is observed that at glass transition temperature exists an
inflexion point. After this point, the glass viscosity decreases,
specific volume abruptly increases, and the specific density has a Fig. 4. Dynamic viscosity of glass vs heating temperature.
greater rate of decreasing. This behavior has major consequences
for design and manufacture of molds. In [3], Fluegel developed
an accurate glass viscosity model relevant to commercial float glasses, TV panel glasses, borosilicate fiber wool and E-type
application through statistical analysis and based on all composi- glasses, low expansion borosilicate glasses, glasses for nuclear
tion–property data available in SciGlass. The viscosity model for waste vitrification, lead crystal glasses, binary alkali silicates, and
predicting the complete viscosity curve of glass was developed various other compositions.
using a global statistical approach and more than 2200 composi- All that is required to make glass is sand, soda, a little lime, and
tion–viscosity data for silicate glasses collected from over 50 years a lot of heat. The typical process of glasses fabrication is shown in
of scientific literature, including soda–lime–silica container and Fig. 6.

Table 1
Types of oxides used in glass fabrication.

No. Oxide type Characteristics Examples

1 Main glass former oxides Suitable structures and low crystallization rates SiO2
B2O3
Form glass under slow cooling rates GeO2
P2O5
2 Conditional glass formers oxides Form glass under certain conditions Al2O3; Bi2O3 WO3; MoO3
3 Intermediate oxides Cannot form glass themselves but form glass in mixture with former oxides TiO2; ZnO; PbO; Zr2O3
4 Network modifier oxides Cannot form glass themselves nether in mixture with former oxides MgO
CaO
Na2O
They can modify the properties of glass by affecting Si–O bonds K2O
1720 E. Axinte / Materials and Design 32 (2011) 1717–1732

Table 2
The standard points of glass.

No. Standard point Viscosity Temperature descriptions

name (Pa s)
1 Working point 103 At this temperature, the viscosity is sufficiently low for glass forming. Casting processes are possibly below 10 Pa s viscosity
2 Softening point 106.6 At this temperature, the viscosity is sufficiently low for glass to slump under own weight. Near below this temperature glass
is stiff, but a little effort is necessary for yield and flow
3 Glass transition 1012 Range of temperatures at which glass transitions from super cooled liquid in a solid state
temperature
4 Annealing point 1013.4 Internal stresses are relieved in minutes
5 Strain point 1013.6 Internal stresses are relieved in hours

1 Pa s (SI) = 0.1 P (P – poise, physics system of units).

tured in glass pieces by different techniques as blowing, molding,

casting, injection, extrusion, and wire drawing.
Commercial glasses are silica-based glasses with additional oxi-
des (see Table 1). The presence, type, and the quantity of one or
many oxides give the glass type and also have major influences
on the glass properties and utilization. For example, a colored glass
is obtaining by addition of a metallic oxide (iron oxide for green
glass, cobalt oxide for blue glass). Crystalline glass–ceramics are
obtained by the introduction of titanium oxide in melted glass.
Titanium oxide initiates the crystallization and the material ob-
tained is up to 96% crystalline [1].
The mechanical and physical properties of glasses are essen-
tially determined by their composition, but a general view can be
given:

a.Glasses are harder than metals.

b.Glasses have tensile strength in the range 24–69 MPa.
c.Glasses are brittle and have low ductility.
Fig. 5. The evolution of specific density vs temperature (———— specific volume vs d.Glasses have a low coefficient of thermal expansion.
temperature). e.Glasses have a low coefficient of thermal conductivity.
f.Glasses are good electrical insulators.
g.Glasses are resistant to acids, solvents, chemicals, water and
The mixture of refined sand (SiO2) and additional basic oxide is saline water and alkaline solutions.
heated in furnace (gas or electric) at a temperature higher than h. Some glasses can be used at high temperatures (700 °C –
1200 °C. Essentially, the main role of this additional oxides (as soda lime for windows; 1580 °C – fused quartz–silica).
CaO, Na2O, K2O) is to reduce the working point of the mixture. A
pure silicone oxide (quartz) is refractory, with a softening point Selection of the main mechanical and physical properties of
near 1500 °C or higher. Then, the melted composition is manufac- amorphous glass and crystalline glass–ceramic is presented in

Fig. 6. Basic technology for glass fabrication (integrated with the recycling process).
 E. Axinte / Materials and Design 32 (2011) 1717–1732 1721

Table 3 A list of glass types in the flat glass industry is starting from ba-
Mechanical properties of glasses vs other engineering materials. sic glass types as float glass, mirrors, and trough security types to
Material Flexural Compressive Hardness, Young special glass types like electrochromic and photovoltaic glass
strength strength HV modulus (see Table. 6). A large spectrum of designer’s interests for these
(MPa) (MPa) of elasticity, glass products are also observed.
E (GPa)
A simplified classification is based on the chemical composition
Silica (amorphous 98 1860 600 69 and follows the crystallization model (Table 7).
glass)
Crystalline 103 344 250 64
glass–ceramic 4.1. Advances in glass and glass–ceramics design and manufacture
Plastic 89.6 2.28
(polycarbonate) In [4], Hampshire revealed some advances in the domain of oxy-
Carbon steel 275 275 100 200
nitride glasses. This work is a complete review of the development
Cemented carbide 1400 4000 1000 612
of oxynitride glasses and outlines the effect of glass composition,
especially nitrogen content and also cation ratios, on properties
and relates this to structural features within the glass. Nucleation
Table 4 and crystallization studies are also outlined. Oxynitride glasses
Physical properties of glasses vs other engineering materials. are prepared by mixing appropriate powders – silica, alumina,
Material Density Thermal Coefficient Electrical the modifying oxide(s) plus silicon nitride or aluminum nitride –
(kg/ conductivity of thermal resistivity in isopropyl alcohol in a ball mill with sialon milling media, fol-
m3) (W/m °C) expansion, (O m) lowed by evaporation of the alcohol. Glasses (50–60 g) are melted
20–100 °C in boron nitride-lined graphite crucibles under 0.1 MPa nitrogen
(10 6 m/m °C)
pressure at 1600–1750 °C for 1 h, after which it is quickly removed
Silica (amorphous 2304 34 1 107 from the furnace and poured into a preheated graphite mold at
glass)
Crystalline 2592 33 9.4 1012
850–900 °C. The glass is annealed at this temperature for 1 h to
glass–ceramic remove stresses and then slowly cooled. The main conclusions of
Plastic 1296 0.2 6.7 8  1014 the study are that oxynitride glass formation occurs in a number
(polycarbonate) of M–Si–O–N, M–Si–Al–O–N and M–Si–Mg–O–N systems, and
Carbon steel 8064 47 11.9 20
8
using normal melting processes, up to 30 equiv.% nitrogen can
Cemented carbide 16,000 86 7.4 6  10
be dissolved in the glass. An innovative approach, using metal pre-
cursors, allows much more N to be dissolved into some M–Si–O–N
glasses. As nitrogen content increases, properties such as glass
Tables 3 and 4. For comparison, in tables are presented some prop- transition temperature, elastic modulus, viscosity, hardness, and
erties of a plastic (polycarbonate), a carbon steel, and a cemented slow crack growth resistance increase while thermal expansion
carbide WC with 6% cobalt. coefficient decreases as a result of increased cross-linking of nitro-
Optical properties of glasses make them preferable in the con- gen within the glass network. Spectroscopic studies have identified
struction of lenses and windows. The very low coefficient of ther- the structural features of glasses and the role of nitrogen as a net-
mal expansion of high silica glasses makes them extremely work ‘‘former’’. Many studies on crystallization of oxynitride
resistant at thermal shocks and also makes them favorite for labo- glasses have been carried out, which have identified suitable
ratory glass instruments (tubes, retorts) and light bulbs. The crys- two-stage heat treatments for nucleation and growth of crystal
talline glass with elasticity modulus above 130  103 MPa has phases, to form glass–ceramics with significant increases in
good shock resistance. strength and elastic modulus over the parent glasses. Addition of
fluorine extends glass formation in oxynitride systems and allows
dissolution of higher levels of nitrogen into glasses. Fluorine lowers
4. Advances in glass family development
glass transition temperature but does not have any effect on elastic
modulus or microhardness. Nitrogen may be dissolved in phos-
The glass family is huge and is in continuous enrichment. Year
phate glasses with consequent improvements in chemical durabil-
after year, new types of glass with new properties extend their uti-
ity and increases in many physical and mechanical properties [4].
lization domain. The utilization domain of glass in engineering de-
New advances in structural glasses domain are described by
sign have a lot of facets: from banal windows or bottles to
Royer-Carfagni and Silvestri [5]. The authors developed an innova-
antinuclear radiation containers; from architectural and structural
tive point-fixing system (called Gecko system) for frameless glass
glasses to photosensitive glass devices used in machine controls;
glazing that exploits the enhanced mechanical properties of a
from food preparation tanks to newest optical fibers.
new generation of ionoplast polymer interlayers. Laminated glass
The enormous variety of existent glass types, rapid develop-
connected with the new device exhibits a noteworthy resistance
ment of new and innovative glasses, developments in glass fabrica-
and interesting post-glass-breakage performances. To achieve a
tion and development of glass-manufacturing processes make the
fail-safe performance, the key point is to attach the polymeric
classification of glasses extremely difficult. After the product types,
interlayer of laminated glass directly to metallic holders, so that
a first classification can be done for the main glass industries, as in
the interlayer itself may act as a confining membrane even after
Table 5 (based on http://www.glassonweb.com/ description-in
glass-breakage. This technology is possible only if the polymeric
section directory).
materials present sufficiently high mechanical properties and ad-
here well to both glass and metals. The Gecko system is presented
Table 5 in Fig. 7 (from [5]).
Classification of main glass industries. After the testing of the system in different conditions (tests at
Main glass industries room temperature, tests on aged samples and tests at low and high
temperatures), the authors have demonstrated that the polymer
Flat Hollow Automotive Art Optical Glass Glass
glass glass glass glass glass fibers Wool can be easily curved by slightly heating the material, and even
when the radius of curvature is very small, no considerable decay
1722 E. Axinte / Materials and Design 32 (2011) 1717–1732

Table 6
Glass types in flat glass industry and the designers spectrum of interests.

Designer’s interests Automotive/ Architecture Physics/chemistry/

aerosapce construction electronics
Flat glass Common glasses (basic and Float glass x
industry decorative) Body tinted glass x
Reflective glass x x
Low glass x x x
Mirror x x x
Insulating glass
Enameled/screen x
printed glass
Pattern glass x x
Antique mirror x
Special glass types Photovoltaic glass x x x
X-ray protection glass x x x
Electrically heated glass x x x
Electrochromic glass x x x
Liquid crystal glazing x x
Self-cleaning glass x x x
Sand-blasted glass x
Acid-etched glass x x
Bent glass x x
Tempered glass x x x
Laminated glass x x x
Fire-resistant glass x x x
Wired glass x x x
Alarm glass x x x
Antireflective glass x x x

Table 7
Simplified glasses classification.

No. Type Description/key words

1 Ordinary – amorphous Amorphous structure; silica base; high commercial spectrum
glasses
a. Quartz
b. Silica glass
c. Na–Ca
silicate glass
2 Glass–ceramics Glass–ceramics are manufactured through the controlled crystallization of a specially formulated glass – a high density of crystalline
nuclei (Ti, Zr, P2O5) is generated in the molten glass. Glass–ceramics are useful in thermally hazardous conditions. Good resistance to
erosion and pressure and the excellent hardness make glass–ceramics widely used in industrial purposes. Moreover, glass–ceramics
are very good electrical insulators
3 Bulk metallic glasses Bulk metallic glasses (BMGs) are metallic materials with a disordered atomic-scale structure, produced directly from the liquid state
BMGs during cooling (the rapid cooling, on the order of millions of degrees a second, is too fast for crystals to form and the material is ‘‘locked
in’’ a glassy state), are called ‘‘glasses’’, or amorphous metals and they are commonly referred as ‘‘metallic glasses’’ or ‘‘glassy metals’’.
BMGs have been paid great attentions for its theoretical and practical reasons since the bulk amorphous Pd–Cu–Si and Pd–Ni–P alloys
was first synthesized by water quenching method in 1974. More recently, batches of amorphous steel have been produced that
demonstrate strengths much greater than conventional steel alloys. The most useful property of bulk amorphous alloys is that they are
true glasses, which means that they soften and flow upon heating. This allows for easy processing, such as by injection molding, in
much the same way as polymers. Bulk metallic glasses have been commercialized for use in medical devices, and as cases for electronic
equipment

of the mechanical properties has been observed. In any case, the study its applications, such as optical amplification or laser oscilla-
viscoelastic nature of the polymer renders the response strongly tion using Bi luminescent materials. Optical amplification around
dependent upon the load duration and environmental tempera- 1.3 lm with Bi-doped multicomponent glass fiber is useful for
ture. However, the confinement effect produced by the attached metropolitan area network optical amplifiers [7].
glass or metal enhances the mechanical strength of the bent A large study about advances in multicomponent silicate
appendix, which results much higher than that of the plain poly- glasses and their glass–ceramics derivatives for dental applications
mer especially at relatively high temperatures. The post-glass- is presented by ElBatal et al. [8]. X-ray diffraction patterns reveal
breakage testing shows that the interlayer remains attached to the formation of lithium disilicate as a major phase together with
the metallic holders even after complete breakage of both glass other subsidiary phases precipitated during the crystallization pro-
plies, thus acting as a confining membrane that prevents the cess according to the other constituent oxides. Infrared spectra
detachment of the glass fragments. show mainly characteristic bands due to silicate network.
In [6], Fujimoto describes a new infrared luminescence from In [9] is statistically analyzed the relation between the chemical
bismuth (Bi)-doped glass. In this work, the author will introduce composition and the density of silicate glass melts at temperatures
the basic properties of Bi-doped silica glass (BiSG), such as a phase of 1000–1400 °C. The analysis was carried out on all 140–260
diagram and spectroscopic properties, and then mainly talk about available values in the SciGlass information system for composi-
the origin of luminescent center. After the discovery of a new infra- tions containing more than 40 mol% silica, less than 40 mol% boron
red luminescent bismuth center, several research groups started to oxide, varying amounts of Al2O3, Li2O, Na2O, K2O, MgO, CaO, PbO,
 E. Axinte / Materials and Design 32 (2011) 1717–1732 1723

Fig. 7. The Gecko system with indication of the bent polymeric interlayer [5]. (a) Section; (b) front view of a prototype.

and other minor components. A model based on multiple regres- calcium oxide increases the glass melt density due to its relatively
sion was developed. The 95% confidence interval of the mean mod- high molecular weight and the moderate influence on the thermal
el prediction on the density was 0.5–3%, depending on the expansion coefficient; lead oxide, PbO, has a very high molecular
composition of interest. The prediction of density as a function of weight; therefore, it increases the glass melt density significantly.
temperature made possible the estimation of the coefficient of An example for glass designer’s use is given in Fig. 8 (from [9]).
thermal expansion in the molten state to within 20–40% error with The authors recommend that for glass design through property
a 95% level of confidence. The effects of the composition of silicate modeling, evaporation losses during glass batch melting and possi-
glass melt density and thermal expansion are investigated: boron ble influences of the oxidation states of transition metal oxides
oxide, B2O3, decreases the density of silicate glass melts based on must be taken into account.
its low molecular mass; lithium oxide, Li2O, slightly decreases Advances in environmental glass industrialization are extracted
the density of silicate glass melts; alumina, Al2O3, clearly increases from [10–12] and are listed as follows: Ref. [10] presents glasses
the glass melt density at high temperatures (1200–1400 °C); so- obtained from melting mixtures of industrial wastes (panel glass
dium oxide, Na2O, does not have a strong influence on the glass from cathode ray tubes, mining residues from feldspar excavation,
melt density within the studied temperature range because of and lime from fume abatement systems of the glass industry). Mi-
the interplay between its medium molecular weight, its influence cro- and macrocellular sintered glass–ceramics were manufac-
on the thermal expansion, and component interactions. At tured. Microcellular glass–ceramics, with a closed porosity, were
1400 °C, adding Na2O appears to decrease the density, whereas at prepared by the direct foaming of the glass mass, determined by
lower temperatures, the influence of Na2O addition is not readily viscous flow sintering of fine powders (<37 lm), due to the addi-
recognized; potassium oxide, K2O, decreases the density of silicate tion of a SiC-based waste (from polished glass articles). The surface
glass melts; magnesium oxide, MgO, might not decrease the glass crystallization of glass, upon sintering, limited the porosity (being
melt density despite its low molecular weight, because it does not about 50%), but imparted a remarkable crushing strength to the
appear to increase the thermal expansion coefficient significantly; products (up to about 80 MPa), useful for construction applica-

Fig. 8. Glass viscosity example curves, derived from experimental data (except lead crystal glass) – from [9].
1724 E. Axinte / Materials and Design 32 (2011) 1717–1732

tions. Micro- and macrocellular glass–ceramics, with an open large-scale manufacturing of glasses that are closely related to cur-
porosity and very low relative density (from 40% to less than rent products, and other applications will require materials re-
10%), were prepared by the sintering of fine glass powders mixed search to develop new compositions and forms that meet
with Polymethyl Methacrylate micro-beads or deposited on poly- stringent engineering requirements.
urethane sponges. The crystallization, besides imparting a good
mechanical strength, allowed the maintenance of the open-celled 4.1.1. Glasses and solar energy
morphology, useful for filtering applications. The production of cel- Solar energy applications include thermal, photovoltaic, and
lular sintered glass–ceramics, both by direct foaming (exploiting a photochemical energy conversion, and the scale of solar systems
SiC-based waste) and by the usage of sacrificial polymeric materi- range from power plants to portable, individual power units.
als, is also illustrated. Intrinsic physical, chemical, and mechanical properties of glasses
Ref. [11] summarizes the progresses and points out the direc- (optical transparency, chemical durability, strength, thermal
tions for the proper uses of waste glasses in Portland cement and expansion coefficient, manufacturability, etc.) make them indis-
concrete. The use of recycled waste glasses in Portland cement pensable for all solar energy systems. The specific function of the
and concrete has attracted a lot of interest worldwide due to the glass component is common to all solar systems: glass transmits
increased disposal costs and environmental concerns. Being amor- desirable solar radiation to an active component (photovoltaic cell,
phous and containing relatively large quantities of silicon and cal- thermal storage unit, etc.) while providing chemical and structural
cium, glass is, in theory, pozzolanic or even cementitious in nature protection of that active component from the ambient conditions.
when it is finely ground. Thus, it can be used as a cement replace- The engineering conditions for glasses in solar energy systems
ment in Portland cement concrete. The use of crushed glasses as are synthesized in Table 8 (adapted from [12]).
aggregates for Portland cement concrete does have some negative The performances of solar power units can be improved by
effect on properties of the concrete; however, particle applicability improving the design of the glass unit. Glass covers for photovol-
can still be produced even using 100% crushed glass as aggregates. taic units can be patterned to help concentrate and guide the solar
The main concerns for the use of crushed glasses as aggregates for energy to the photovoltaic layer. Reflective layers coated on the
Portland cement concrete are the expansion and cracking caused patterned, back surface of the cover further guide solar radiation
by the glass aggregates. to the photovoltaic cells by means of total internal reflection. Mir-
National Academy of Engineering (NAE – Washington, DC) iden- rors are commonly used in solar power units, and researchers try
tified glass and glass–ceramics as central to many of the great engi- to find the best solutions for improving their durability and effi-
neering achievements of the 20th century, as development of solid ciency (silvered glasses, polymer-coated sheet aluminum, silvered
state lasers and optical glass fibers, biomaterials, glasses for imag- polymer films). Other solar power applications drive to important
ing technologies, glass films in microelectronic devices [12]. In glass development and manufacturing as building-integrated
2008, NAE also identified The Grand Challenges for Engineering photovoltaic (BIPV). BIPV have been developed to incorporate
for 21st Century (Fig. 9). energy-efficient structures into building fronts and facades and
Some of these challenges offer great opportunities for glass sci- are produced by encapsulating and alternating with transparent
entists and manufacturers to develop their role of improving the resin solar cells between glass sheets. In this way is producing elec-
human condition, to contribute to the development of new and tricity and is reduced solar heat gain while still allowing daylight
sustainable sources for energy and to develop techniques that en- to enter the building. Because of their large thermal inertia, glasses
hance the environment. are used in other forms to rapidly capture solar energy and to
A complete survey of environmental, energy-saving and pro- release them slowly: hollow glass beads, glass wool, etc. The inte-
duction applications of glasses is given by Brow and Schmitt gration of inorganic synthetic methods with a size reduction to the
[12]. In this paper, authors review some of the opportunities for nanoscale has lead to the creation of a new class of optical report-
the development and use of glass to address future energy and ers, called quantum dots. These semiconductor quantum dot nano-
environmental challenges. Some of these applications will require crystals have emerged as an alternative to organic dyes and

Fig. 9. Schematics of The Grand Challenges for Engineering for 21st Century (adapted from [12]).
 E. Axinte / Materials and Design 32 (2011) 1717–1732 1725

Table 8
The engineering conditions for glasses in solar energy systems (adapted from [12]).

Desired Descriptors Research, development and design challenges

properties
Optical properties  Maximum transparency over desired wavelength of Compositional control for trace transition metal contents
solar light (UV, IR)
 Reduced refractive index (for minimum reflection loss) Nanocomposites, glasses and glass–ceramics with engineered transparencies
 Filtering non-desirable UV wavelengths New materials for optically active substrates (infrared luminescence)
 No solarization effects
Mechanical  Minimum density at maximum strengths Stronger, ‘less brittle’ glasses and glass–ceramics
properties  Improve fracture toughness Thermal/chemical/mechanical treatments to improve strength and resistance at
environmental events (sand storms, etc.)
 Thermal expansion characteristics of system
Chemical  Maximized weathering resistance Improved resistance at corrosion to acid rains or environmental salinity
properties
Manufacturing  Viscosities, thermal stabilities that complement specific New manufacturing techniques for customized designs and compositions
properties manufacturing process

fluorescent proteins and are brighter and more stable against 4.1.3. Glass for water desalination and hydrogen production
photobleaching than standard fluorescent indicators. Quantum Transparency to solar radiation is essential for solar collection
dots have tunable optical properties that have proved useful in a systems and thus solar stills generally consist of glass covers. The
wide range of applications from multiplexed analysis such as glass covers also act as condensation surfaces and are usually
detection of nucleic acids (DNA) and cell sorting and tracking to angled to aid in distillate collection. The most basic types of solar
most recently demonstrating promise for in vivo imaging and diag- stills are single and double basin (Fig. 10 – adapted and modified
nostics [14]. By introducing quantum dots (crystalline, semicon- from [12]).
ductor nanostructures, as CdSe/ZnS, which absorb light and emit In [13] authors describes the using of amorphous silicone car-
photons of lower frequencies) directly in transparent glass matrix bide for construction of an photoelectrode for hydrogen production
or in films incorporated by glass sheets are obtained solar collec- (SiC:H) using the sun light. The simulation results which indicate
tors that can be integrated in building facades. that a SiC:H as a photoelectrode in a photovoltaic (PV – SiC:H)
structure could lead to a efficiency of solar heat conversion greater
than 10% are also presented.
4.1.2. Glasses and water purification
Solar-driven technologies make use of glass as substrates for 4.1.4. Glasses and wind energy
photocatalytic decontamination methods, and glass windows and Glass fibers reinforced composites are commonly used for wind
tubes enable the operation of both photocatalytic and desalination turbines. The fatigue resistance of these composites is crucial for
systems for producing clean water. Photocatalysis using glass sub- the maintenance and reliability of turbine. That gives the opportu-
strates – the electrophoretic coating method – was used to deposit nity for designers to create new, ultra-high strength, high-modulus
titania onto glass substrates that had been coated with indium- glass compositions for these applications, including environmen-
doped tin oxide to improve conductivity. The glass substrates were tally friendly, boron-free glasses. In [15], authors made a compar-
found to have a significant advantage over other options due to ison at chemical attack for basalt and E-glass fibers, under a
their transparency to UV-A light and their chemical stability. This complex chemical attack. Basalt and glass fibers were treated with
transparency allows for illumination from either side of the coating sodium hydroxide and hydrochloric acid solutions, respectively, for
and increases the surface area available for photocatalysis. Further different periods of time. Both the mass loss ratio and the strength
improvements in efficiency could be realized when glass sheets are maintenance ratio of the fibers were examined after the treatment.
replaced by glass beads and fiberglass mesh to increase the active Some results, obtained under acid attack conditions are presented
surface areas of the photo-reactors. in Figs. 11 and 12 (reproduced from [15] – ÓElsevier).

Fig. 10. Double basin solar still for desalination (adapted and modified from [12]).
1726 E. Axinte / Materials and Design 32 (2011) 1717–1732

For the basalt fibers, the acid resistance was much better than strength is still low and shows the potential for utilization of hy-
the alkali resistance. Nevertheless, for the glass fibers, the acid brid natural fiber in some car structural components such as bum-
resistance was nearly the same as the alkali resistance. per beams. The comparison charts (Fig. 13) show some mechanical
Technical report [16] proposes a hybrid glass–reinforced epoxy properties advantages (higher elasticity and tensile/flexural
composite as a good material for Passenger Car Bumper Beam. Envi- strengths) and disadvantages (lower impact resistance and higher
ronmental constrains make the hybridization of synthetic with mass density) of hybrid material vs the common bumper beam
agro-based structures become a reality in the near future. These material (GMT).
hybrids are designed for non-structural and semi-structural com-
ponents. Experimental setup from [16] is focused on a hybrid of ke- 4.1.5. Glasses as immobilizers for nuclear wastes
naf/glass fiber to enhance the desired mechanical properties for car A big challenge in nuclear-related industries is that the radioac-
bumper beams as automotive structural components with modi- tive wastes generated must be isolated and safely stored. Glass is
fied sheet molding compound (SMC). In this research, authors de- the material of choice for waste forms because it can be designed
velop a hybrid material using natural kenaf and synthetic glass with good chemical durability, good mechanical properties, and
fiber as reinforcement. Kenaf is extracted from the bast of the an- superior radiation and thermal stability than other waste forms.
nual fast-growing plant named Hibiscus cannabinus. The main con- The vast compositional variability of glass makes it possible to
stituents of kenaf are cellulose (45–57 wt.%), hemicelluloses incorporate the many different nuclear waste compositions, and
(21.5 wt.%), lignin (8–13 wt.%), and pectin (3–5 wt.%). E-glass fiber glass forming and processing allow for easy, large-scale production
has been extensively applied as a reinforcement in polymer com- of waste forms. For these dangerous wastes, as immobilizers are
posite, and its good mechanical properties and low price are generally used the borosilicate glasses. Borosilicate glass is a
important considerations. Epoxy is selected as the matrix for the particular type of glass, known under the brand names Pyrex or
hybrid material. A specimen without any modifier is tested and Kimax. It was first developed by German glassmaker Otto Schott
compared with a typical bumper beam material called glass mate- in the late 19th century and sold under the brand name ‘‘Duran’’
rial thermoplastic (GMT). The results indicate that some mechani- in 1893. After Corning Glass Works developed Pyrex in 1924, it be-
cal properties such as tensile strength, Young’s modulus, flexural came a synonym for borosilicate glass in the English-speaking
strength, and flexural modulus are similar to GMT, but impact world [17]. Borosilicate glass is the oldest type of glass to have
appreciable resistance to thermal impact and higher temperatures
and also has excellent resistance to chemical attack. In this glass
structure, a little of the SiO2 is replaced by boric oxide B2O3 (13%).
Typical algorithm process in vitrification facilities for radioac-
tive wastes is shortly presented below: radioactive elements are
separated from the waste stream, mixed with a borosilicate glass
frit, and melted at 1200 °C; the molten waste glass is cast into
large stainless steel canisters (approximately 1500 kg each); the
canisters are decontaminated, welded shut, and stored at the vitri-
fication facility; the canisters are moved to geological repositories
[18]. Recent, the iron phosphate glasses are investigated as alterna-
tive for nuclear waste immobilizers and are considered a ‘‘high pri-
ority for US Department of Energy – DOE’’ [19]. Studies revealed
that iron phosphate glasses have excellent chemical durability,
and some compositions have corrosion rates 1000 times lower
than borosilicate waste glass.

4.1.6. Glasses as energy storage systems

Fig. 11. Mass loss ratio-treating time behavior (acid treatment) (reproduced from
The possibilities to engineer and fabricate a material with a par-
[14]). ticular set of thermal, electrical, and chemical properties, into a
strictly defined geometry, make from glass a crucial material to en-
able these technologies for energy storage.
Glasses play important roles in smaller power supplies, includ-
ing dielectrics for super-capacitors, electrolytes for electrochemical
devices, and sealants for high-temperature solid oxide fuel cells
(SOFC). In [20], glass–ceramic sealants free from barium oxide
(BaO) and sodium oxide (Na2O) have been designed and investi-
gated in the crystallization field of diopside (CaMgSi2O6). Further,
the influence of Bi2O3 (different amounts 1, 3 and 5 wt.%) addition
on the flow properties, sintering, and crystallization behavior along
with electrical conductivity and long-term thermal stability of
sealants has been investigated. The investigated glass–ceramic
compositions were highly effective in performing metal-to-metal
sealing with smooth interface and negligible interfacial reactions,
thus proving them to be potential sealants for applications in SOFC.
The amount of amorphous character in the glass–ceramics in-
creases during prolonged heat treatments at SOFC operating tem-
peratures, which can be beneficial to provide self-healing ability
to the sealant.
Fig. 12. Strength maintenance ratio-treating time behavior (acid treatment) Glass–ceramics are suitable for use in super-capacitors, and
(reproduced from [15]). some glasses are investigated as solid electrolytes in lithium
 E. Axinte / Materials and Design 32 (2011) 1717–1732 1727

Fig. 13. Comparison charts of mechanical properties GMT vs Hybrid (adapted from [16]).

batteries. A recent study of controlled crystallization of lithium vidual sphere contains a small volume of hydrogen to be hazardous
aluminum silicate (LAS) glass–ceramic shows that with the opti- if the sphere break; (c) HGMS are strong due to their small size and
mum nucleating agents (2%ZrO2 + 2.36%TiO2), LAS glass–ceramics are able to contain hydrogen at high pressures – up to 100 MPa; (d)
with fine grain, high transparency and good mechanical properties no additional transportation vessel is needed, so they serve as
were obtained, due to the b-quartz solid solution formed after the lightweight containers for relatively high hydrogen mass density;
crystallization process [21]. A simple and low cost manufacturing (e) HGMS are reusable and recyclable. For loading with hydrogen,
technique for obtaining the glass–ceramic matrix composites is the glass spheres (produced by different methods, as flame spray
described as follows [22]: sintering with simultaneous crystalliza- pyrolysis of glass frit) are inserted into a high-pressure hydrogen
tion of fine glass powders allowed the preparation of dense environment and are heated enough for diffusion of hydrogen into
glass–ceramics based on unusual feldspar crystals, at a very low spheres. The loaded spheres are extracted from hydrogen environ-
temperature (750 °C) and with limited processing times. Al2O3 ment and cooled at ambient temperature.
platelets were added to the glass powders. The observed effects
are improvement in bending strength (exceeding 100 MPa), 4.2. Advances in bulk metallic glasses (BMG) design and manufacture
microhardness (approaching 9 GPa), and fracture toughness – even
for limited concentrations (which varied from 5 to 15 vol.%). The Metallic glasses exhibit unique softening behavior above their
elastic modulus and coefficients of thermal expansion (CTE) are glass transition, and this softening has been increasingly explored
major contributors to the stresses that can lead to cracking of the for thermoplastic forming of metallic glasses. Metallic glasses can
seal. The model presented by Milhans et al. [23] is useful for be patterned on extremely small-length scales ranging from
designers of glass–ceramic SOFC seal materials : the effective elas- 10 nm to millimeters. It is possible that this may solve the prob-
tic properties and CTE of a glass–ceramic were predicted using lems of nanoimprint lithography where nanomolds made of silicon
homogenization techniques. Using G18 (a glass–ceramic SOFC break easily. Nanomolds made from metallic glasses are easy to
sealant) as an initial reference material, the effectiveness of differ- fabricate and more durable than silicon molds [24]. The process
ent homogenization models was investigated for a two-phase of making nanoscale devices by simple stamping or molding may
glass–ceramic. The predictive model offers accurate macroscopic revolutionize the manufacture of nanodevices from computer
values on both the elastic modulus and the CTE of glass–ceramic memory to biomedical sensors.
materials, provided the estimated amorphous values are Metallic glass (Ti40Cu36Pd14Zr10) is considered non-carcino-
reasonable. genic, is about three times stronger than titanium, and its Young’s
Hollow glass bubble technology was developed by 3M in the Modulus matches bones. It has a high wear resistance and does not
1960s, and today this material is used in aerospace and military produce abrasion powder. The alloy (Mg60Zn35Ca5) rapidly cooled
systems, paints and coatings, marine hulls, oil and gas exploration to achieve amorphous structure (BMG) is being investigated as a
and production and other industrial uses. Glass bubbles are made biomaterial for implantation into bones as screws, pins, or plates,
from a chemically stable soda–lime borosilicate glass and pro- to fix fractures [25].
duced in a range of properties, including nominal diameters from The first reported metallic glass was an alloy (Au75Si25) pro-
9 lm to 70 lm, densities from 0.15 to 0.60 g/cm3, and compressive duced at Caltech by Klement Jr., Willens, and Duwez in 1960. This
strength ratings from 1.7 MPa to 20 MPa. Resin compounder Noble and other early glass-forming alloys had to be cooled extremely
Polymers (Grand Rapids, Michigan, subsidiary of Cascade Engineer- rapidly (on the order of 1  106 K/s) to avoid crystallization. An
ing) has developed a low-density polyolefin resin formulation that important consequence of this was that metallic glasses could only
reduces the weight of thermal plastic olefin (TPO) parts by up to be produced in a limited number of forms (typically ribbons, foils,
twenty percent. This masterbatch bulk resin additive incorporates or wires) in which one dimension was small so that heat could be
hollow glass bubbles from 3M Company to displace resin and re- extracted quickly enough to achieve the necessary cooling rate. As
duce part density in injection molded, thermoformed, and ex- a result, metallic glass specimens (with a few exceptions) were
truded thermoplastic parts. limited to thicknesses of less than 100 lm. Bulk metallic glasses
Recently, hollow glass micro-spheres (HGMS) are considerate as have been paid great attentions for its theoretical and practical rea-
a viable alternative for hydrogen storage [12]. Some advantages for sons since the bulk amorphous Pd–Cu–Si and Pd–Ni–P alloys was
using HGMS as hydrogen storage and transportation containers are first synthesized by water quenching method in 1974.
(a) the materials are cheap and most of the batch consists of recy- Ref. [26] describes how copper was inserted into hard magnetic
cled cullet; (b) the micro-spheres are non-explosive and each indi- bulk metallic glass Nd–Fe–Al alloys. The effects on the magnetic
1728 E. Axinte / Materials and Design 32 (2011) 1717–1732

properties and glass-forming ability (GFA) were assessed using glass systems. Some techniques as CALPHAD predict and describe
vibrating sample magnetometer and thermal expansion method. well the glass-forming and new glass-forming composition regions
The as-cast alloys exhibited higher GFA ability and hard magnetic in some multicomponent alloy systems. The authors final conclu-
properties at room temperature. The enhancement of GFA is attrib- sion are that the formation of metallic glass is a non-equilibrium
uted to more negative mixing heat between Cu and Nd, and process, and studies in view of equilibrium theories may lead to
accordingly, less crystallite and more Fe-rich clusters result in incorrect results and that is a long way to develop proper indica-
higher coercivity up to 313 kA/m. Adding more Cu, however, will tors for GFA, which are theoretically strict and composed of very
cause an abrupt reduction in coercivity for the precipitation of soft simple and fundamental parameters.
magnetic and non-magnetic crystalline phase.
The effects of alloy addition on the glass-forming ability, ther- 4.3. Advanced techniques of manufacturing for glass and glass–
mal stability, and mechanical properties of Mg–Cu–Tb-based bulk ceramics
metallic glasses were investigated in [27]. The Mg-based BMG have
received intensive attention due to their high specific strength and Sometimes, glass pieces require some supplementary opera-
relatively low cost. Mg–Cu-based BMG could be fabricated by con- tions as drilling, cutting, grinding, and stamping for meeting their
ventional copper mold casting method in air atmosphere without functional or aesthetic role.
obviously decreasing the GFA. These BMGs exhibit higher specific The mechanical and physical properties of glasses (especially
strength comparing to their crystalline counterparts. In [27], brittleness and low ductility) make them very difficult or impossi-
authors investigated the effects of alloy additions on the GFA and ble to manufacture them by conventional mechanical processes.
mechanical properties of a typical glass-forming composition, Drilling of holes in glasses is possible to non-tempered glasses
Mg65Cu25Tb10, which approaches the ideal brittle behavior associ- and ceramics. The glass bits have a spade-shaped point and are
ated with silicate glasses The authors demonstrate that appropri- made of tungsten carbide to withstand the friction of drilling in
ate additions of Ag, Zn or Be in Mg65Cu25Tb10 could not only glass. Diamond drillers are also used for holes with diameter smal-
improve the glass-forming ability but also enhance the strength ler that 10 mm.
and plasticity of these amorphous metallic alloys within a certain Conventional glass cutting is done by scoring and breaking
composition range. which produces micro-cracks and splinters and leaves cutting oil
Zirconium-based metallic glasses (Zr-based BMG) present good residues. These influences lead to lowered strength and pollution
mechanical properties that combines the high fracture stress, elas- of the glass sheets. If the glass has to be tempered, further grinding,
tic strain (up to 2%), significant fracture toughness, and good corro- polishing, and washing processes are needed.
sion resistance. In [28] is studied the influence of aluminum Cutting still remains one of the most common operations for
content on the GFA and on the mechanical properties of the glasses. Old-fashioned hand-cut glass remains indispensable for
Zr–Ni–Cu–Ti alloys. Multicomponent Zr75 xAlxNi10Cu10Ti5 any glass-processing workshop but today’s technologies allow us
(x = 15–20 at.%) alloys were produced by melt spinning method to cut glass with machines.
obtaining ribbons, and by casting technique into a copper mold, Waterjet cutting technology can be described as a controlled
manufacturing rod-shaped samples with a maximum diameter of accelerated erosion process. This system consists of high-pressure
2 mm. Supercooled liquid region depends on chemical composition water, mixed with abrasives, that passes through a gauge orifice at
and exceeds 45 °C. Vickers microhardness of studied alloys is three times the speed of sound. Such pressure produces a pure
comparable to the highest ones for other Zr-based BMG. working power able to cut any shape of glass or other materials.
The glass-forming ability (GFA) is one of the most important In comparison with the traditional diamond cutting system, it
factors in the study of metallic glasses. No standard definition has the following advantages: flexibility, high accuracy, works on
has been made for this parameter up to now, and many indicators any material, low cost, lack of heat generation. Short communica-
have been developed. A review of advances in characterization of tion [30] reports a particular application of abrasive waterjet (AVJ)
GFA is given by Bing et al. [29]. In this work, four types of criteria turning that proved its technological and economical capability, i.e.
for the glass-forming ability are categorized and reviewed: (1) profiling and dressing of grinding wheels with ceramic bonds. The
indicators with characteristic temperatures; (2) indicators involv- schematic process and the experimental setup and is described by
ing structural factors; (3) indicators based on Miedema’s model; Fig. 14 (adapted from [30]).
and (4) indictors based on phase diagram. Authors underline that The results are very suggestive illustrated by Fig. 15. This tech-
a single indicator cannot be used to predict GFA of all the metallic nology seems to be attractive for those manufacturing sectors for

Fig. 14. The illustration of abrasive waterjet turning.

 E. Axinte / Materials and Design 32 (2011) 1717–1732 1729

Fig. 15. Some results of waterjet turning.

roughing and semi-finishing off-the-shelf grinding wheels for the glass tolerates only a certain amount of energy per square per time.
production lines that require mass utilization of specially profiled If this value is too large, the glass breaks or gets a grainy structure
grinding wheels. in the heated zone. To meet this requirements, many patents are
Laser cutting of flat glass is a subject of a handful of specialists. known, all of them try, by forming a special laser spot, to optimize
In practice use for daily production, today there are approximately the energy placement. The invention called LiST (laser-induced
50 installations for flat glass laser cutting worldwide and the same scoring by tension – Grenzebach Maschinenbau GmbH) has to con-
number in research laboratories. The main problem is that the trol not only the laser energy and spot size but also its timing in a
way that more heat on the glass surface can flow to deeper areas
into the glass, where finally a multiplicative energy rate can create
many times higher tension in the glass (see Fig. 16 – from [31]).
The technical limit in cutting speed is the mechanical possibility
to move a small cooling head along the score trace. There is an eco-
nomical limit too: double speed requires double laser power,
which is very expensive to buy.
Development of advanced ceramics has gained significant
importance because of their desirable properties. Their engineering
applications are still limited owing to the limitations in developing
optimized (minimum damages, high rate of material removal, min-
imum roughness, etc.) machining techniques.
In [32], a cylinder from magnesium–silicon-vitrified ceramic
(Steatite 63–63 HRC with initial surface roughness Ra = 3.25 lm)
was plunge grinded with a ceramic bonded abrasive wheel (66A
16K 5 V217 – pink Al2O3). At constant work piece velocity
(vw = 14 m/min) and constant plunge feed (ft = 0.03 mm/min), dif-
ferent cutting speeds were used (vd = 30; 50 and 70 m/s). Good re-
sults was revealed at cutting speed 70 m/s by obtaining a final
surface roughness Ra = 0.8 lm and a finished surface as in Fig. 17b.
Experimental study [33] investigates the grinding characteris-
Fig. 16. Laser-induced scoring by tension – schematic method (from [31]).
tics and surface and subsurface integrity of ground silicon carbide

Fig. 17. Microscopic views of brut (a) and finished (b) ceramic surfaces (from [32]).
1730 E. Axinte / Materials and Design 32 (2011) 1717–1732

to explore the material removal and damage formation mecha- very well by Fig. 19 (adapted from [35]). It is based on the use of
nisms involved during high removal rate grinding. The experimen- thermoplastic polymer spin coated on the substrate. The thermo-
tal investigations revealed that an increase in material removal plastic polymer is heated above the glass transition point of the
rate did not affect surface finish and surface morphology. polymer, and the heated template is brought into contact with
Imprinting technology is an ancient technique for the reproduc- the polymer. Once the polymer has filled all the cavities of the tem-
tion of writings on appropriate supports. Since 1990s, one of the plate, the substrate and the template are cooled down and the tem-
imprinting techniques, i.e., injection molding, has been used for plate is separated from the substrate. A negative replica of the
compact disk (CD) production. More recently, the semiconductor template is created on the polymer. In order to use imprinted poly-
industry is interested in imprint related techniques because of mer for pattern transfer to other layers on the substrate, polymer
the mass production requirement of future microelectronic circuits left on the indented areas has to be removed. Because the flow of
with a possible critical dimension down to a few nanometers [33]. the polymers is not free of resistance, a residual layer appears
Up to now, the process has found its way into scientific research (Fig. 19d).
domains and production lines in micro-optics (Fig. 18) and into
prototyping for nanophotonics and biotechnology and is also ex-
5. Conclusions and strategic lines in glass development
pected to have additional impact in fabrication of memory devices
and in display technology.
Glass as a material will always exist, but many new applications
Nanoimprint lithography (NIL) was introduced in 1995 by
and manufacturing processes will involve glass in combination
Stephen Chou. He demonstrated results from an experiment where
with other materials. Optical fibers are currently manufactured
a laboratory press was used to press together a patterned stamp,
with one or more different coating, which are often plastics. With
made from a SiO2-coated Si-wafer, with a silicon substrate coated
the increasing sophistication of optoelectronic devices, there is an
with a thermoplastic polymer [34]. The NIL process is described
increasing need to combine optical and electronic devices for many
applications such as transmission of audio, video, and data infor-
mation. Glasses and ceramics (stand-alone or composite with other

Fig. 18. 300-mm soft stamp replicated lens wafer and 200-mm stacked wafer level
camera module (from [33]). Fig. 20. Foil of flexible ceramic ZircoFlex™.

Fig. 19. The thermal nanoimprint lithography (adapted from [33]).

 E. Axinte / Materials and Design 32 (2011) 1717–1732 1731

Table 9
Criteria for material selection.

Criteria Ratings
1 Supply property (depletion time, years) A < 25; B – 25 to 50; C – 51 to 100; D > 100
2 Recycled supply property (% of recycled material used) A – 100; B – >50; C – 25 to 50; D < 25
3 Embedded energy property, MJ/kg of material A < 50; B – 50 to 99; C – 100 to 200; D > 200
4 Environmental impact property, scorecard hazard rating A < 25; B – 25 to 50; C – 51 to 75; D > 75
5 Legal property (legal restrictions) A – no problems; B – minor problems; C – serious legal problems; D – under severe legal restriction
6 Longevity (grade of degradation in environment) A – quickly degrades; D – unlimited lifetime
7 Recyclable property (% material recyclable) A – 100; B – 50 to 100; C < 50; D = 0
8 Social and political property A – no social or political problems; D – social malign; political restrictions

materials) will find increasing application in biological and medical The modern glass industry must increase contribution through
areas. Materials such as photochromic, electrochromic, and ther- development and the introduction of new energy-efficient glass
mochromic glasses, which respond to external stimuli, are being products and applications, some issues in glass manufacturing
developed with various, sometimes unusual, applications. Revolu- and processing still must be addressed in the future.
tionary materials, as the flexible ceramic heat shield material (Zir-
coFlex), are recently developed and fabricated by using a new
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